CN106573238B - The chelating resin of the aminomethylation of sulfonation - Google Patents

The chelating resin of the aminomethylation of sulfonation Download PDF

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CN106573238B
CN106573238B CN201580044321.4A CN201580044321A CN106573238B CN 106573238 B CN106573238 B CN 106573238B CN 201580044321 A CN201580044321 A CN 201580044321A CN 106573238 B CN106573238 B CN 106573238B
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chelating resin
functional group
structural element
phthalimide
hydrogen
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CN106573238A (en
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赖因霍尔德·克利佩尔
斯特凡·诺伊法因德
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Lanxess Deutschland GmbH
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
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Abstract

The present invention relates to the chelating resins of the aminomethylation of sulfonation, the method for producing it, are used to from aqueous solution and organic liquid obtain and purified metal, especially rare earth metal, and the purposes for producing high purity silicon.

Description

The chelating resin of the aminomethylation of sulfonation
The present invention relates to the chelating resin of the aminomethylation of sulfonation, for the method for its preparation and its be used for from water-soluble Recycling and purified metal, especially rare earth element in liquid and organic liquid, and it is used to prepare the purposes of high purity silicon.
Novel chelating resin is the target of further investigation, because they have for example in Water warfare or the neck of recycling metal In domain it is significant use potentiality.
EP-A 1078690 discloses a kind of chela for being used to prepare and being suitable for adsorbing the aminomethylation of heavy metal and noble metal The method of resin.This method especially includes for by the SO in catalytic amount3Phthalimide in the presence of donor The hydrolysis of reaction and subsequent acid-or base-catalyzed with formalin and the step of introduce aminomethyl group.In addition to used SO3Only have outside the fact that catalytic effect, is avoided so far using a greater amount of SO3, so as not to endanger the O-phthalic just formed The Structure and stability of the resin of acid imide methylation.
It has been found that unexpectedly, using significant a greater amount of SO3Catalysis is not only allowed for introduce phthalimide Methyl, but also allow to the resin sulfonation simultaneously without the structure of the substantial damage resin.
Therefore the present invention provides a kind of chelating resin of functional group comprising structural element (I)
WhereinIndicate polymer backbone and R1And R2Expression-CH independently of one another2COOX、-CH2PO(OX1)2、- CH2PO(OH)OX2、-(CS)NH2、–CH2Pyridyl group or hydrogen, wherein R1And R2It cannot all be simultaneously hydrogen and X, X1、X2Each other with Y Independently indicate hydrogen, sodium or potassium.
Work as R1And R2It is-CH independently of one another2PO(OX1)2、-CH2PO(OH)OX2、CH2COOX or when hydrogen be it is preferred, Middle R1And R2It cannot all be simultaneously hydrogen.Work as R1It is hydrogen ,-CH2PO(OX1)2Or-CH2PO(OH)OX2And R2It is-CH2PO(OX2)2 Or-CH2PO(OH)OX2When be particularly preferred.Work as R1It is hydrogen and R2It is-CH2PO(OX2)2Or-CH2PO(OH)OX2When right and wrong It is often particularly preferred.X,X1、X2Indicate hydrogen, sodium or potassium independently of one another with Y.As X, X1And X2It is when expression hydrogen independently of one another Preferably.X1And X2It is preferably identical.Y preferably indicates hydrogen.
When being preferred when the phenyl ring in structure formula (I) is replaced on the ortho position of methylene by sulfonic acid group.
The present invention further comprises the method for the chelating resin that one kind is used to prepare the functional group comprising structural element (I)
WhereinIndicate polymer backbone and R1And R2Expression-CH independently of one another2COOX、-CH2PO(OX1)2、- CH2PO(OH)OX2、-(CS)NH2、–CH2Pyridyl group or hydrogen, wherein R1And R2It cannot all be simultaneously hydrogen and X, X1、X2Each other with Y Independently indicate hydrogen, sodium or potassium,
The method is characterized in that it includes：
A) will by least one single-ethenyl aromatic compound and at least one polyvinyl aromatics and The monomer droplet that at least one initiator or initiator combination are constituted is converted into bead polymer,
B) make the bead polymer phthalimide methyl with phthalimide in the presence of oleum Change and sulfonation, wherein free SO3Phthalimide of the amount based on 1mol be at least 0.69mol,
C) bead polymer of the sulfonation of the phthalimide methyl is converted to the pearl of the sulfonation of aminomethylation Shaped polymer, and
D) bead polymer of the sulfonation of the aminomethylation is made to react to provide the functional group for including structural element (I) Chelating resin.
The chelating resin of functional group comprising structural element (I) is preferably characterized in that the method for its own preparation.
Therefore, the present invention also provides the chelating resins of the functional group comprising structural element (I)
WhereinIndicate polymer backbone and R1And R2Expression-CH independently of one another2COOX、-CH2PO(OX1)2、- CH2PO(OH)OX2、-(CS)NH2、–CH2Pyridyl group or hydrogen, wherein R1And R2It cannot all be simultaneously hydrogen and X, X1、X2Each other with Y Independently indicate that hydrogen, sodium or potassium, these chelating resins are prepared in the following manner：
A) will by least one single-ethenyl aromatic compound and at least one polyvinyl aromatics and The monomer droplet that at least one initiator or initiator combination are constituted is converted into bead polymer,
B) make the bead polymer phthalimide methyl with phthalimide in the presence of oleum Change and sulfonation, wherein free SO3Phthalimide of the amount based on 1mol be at least 0.69mol,
C) bead polymer of the sulfonation of the phthalimide methyl is converted to the pearl of the sulfonation of aminomethylation Shaped polymer, and
D) bead polymer of the sulfonation of the aminomethylation is made to react to provide the functional group for including structural element (I) Chelating resin.
Chelating resin for purposes of the present invention is based at least one single-ethenyl aromatic compound and at least one The polymer of kind polyvinyl aromatics.When chelating resin for purposes of the present invention is by styrene, divinyl It is preferred when the polymer that base benzene and ethyl styrene are constituted.
The scope of the present invention include it is all in the above and below, as it is being quoted or in preferred range, be in Group definition, parameter and the explanation of any desirable combination with one another, that is, including especially generally between preferred range Group definition, parameter and explanation.
At least one single-ethenyl aromatic compound and at least one polyvinyl fragrance are used in method and step a) Compounds of group.It is also possible, however, to use the mixture of two or more single-ethenyl aromatic compounds or two kinds or more The mixture of a variety of polyvinyl aromatics.
For purposes of the present invention, for the single-ethenyl aromatic compound in method and step a) be preferably styrene, Vinyltoluene, ethyl styrene, α-methylstyrene, chlorostyrene, 1-chloro-4-methyl-benzene, alkyl acrylate or methyl-prop Olefin(e) acid Arrcostab.
Particularly preferably using styrene or styrene and above-mentioned monomer, preferably with the mixture of ethyl styrene.
It for purposes of the present invention, is divinyl for the preferred polyvinyl aromatics in method and step a) Benzene, divinyl toluene, trivinylbenzene, divinyl naphthalene, trivinyl naphthalene, 1,7- octadiene, 1,5- hexadiene, dimethyl Acrylic acid glycol ester, trimethylol-propane trimethacrylate and allyl methacrylate, particularly preferred divinyl Benzene.
Mixture based on monomer or itself and other monomers, polyvinyl aromatics are preferably with 1%- by weight 20%, the amount use of more preferably 2%-12% by weight, particularly preferably 4%-10% by weight.Polyvinyl aromatic The type of object (crosslinking agent) is closed to be selected in order to which the later period of the bead polymer uses.The case where using divinylbenzene Under, it further include the divinylbenzene of the business level of vinyl xylene, ethyl vinyl benzene and the isomers of divinylbenzene is enough.
Term " bead polymer " for purposes of the present invention is the cross-linked polymer in pearl form.
Term " micropore " or " in gel form " and " macropore " have already been described in detail in the document of profession.
Inert material (preferably at least a kind of pore generating agent) by being added to by the bead polymer of macropore in the course of the polymerization process It is formed in monomer mixture to generate macroporous structure in bead polymer.Suitable pore generating agent includes for being formed by pearl Shaped polymer is the organic solvent of poor solvent and/or sweller.Especially preferred pore generating agent is hexane, octane, isooctane, different Dodecane, methyl ethyl ketone, butanol or octanol and their isomers.Specially suitable substance is dissolved in the monomer but hardly possible In organic matter (precipitating reagent of the polymer) such as aliphatic hydrocarbon (Farbenfabriken for dissolving or being swollen the bead polymer Bayer DBP 1045102,1957；DBP 1113570,1957).
US 4 382 124 uses the alcohol with 4 to 10 carbon atoms as pore generating agent, in the context of the present invention, these Alcohol is also, it is preferred that be used to prepare the bead polymer of styrene-based/divinylbenzene monodisperse, macropore.In addition, giving The summary of the preparation method of bead polymer for macropore.
It is preferred when at least one pore generating agent is added in method and step a).These bead polymers and include structure The chelating resin of the functional group of element (I) preferably has macroporous structure.
According to method and step a) preparation bead polymer can by it is miscellaneous dispersion or it is monodispersed in the form of be produced.
By conventional method known to those skilled in the art, such as miscellaneous dispersion bead polymer is completed by means of suspension polymerisation Preparation.
Preferably monodisperse bead polymers are prepared in method and step a).
In this application, monodisperse material be wherein by volume or by mass at least 90% particle have most often See those of the diameter in+10% range of diameter material.
For example, by volume or by mass at least 90% is with the material of the most common diameter of 0.5mm In size range between 0.45mm and 0.55mm；With the material of the most common diameter of 0.7mm, by volume Or by mass at least 90% be in size range between 0.77mm and 0.63mm.
In a preferred embodiment of the present invention, in method and step a), the monomer droplet of microencapsulation is used to prepare list Disperse bead polymer.
The material useful for monomer droplet microencapsulation is to be known to be used as those of complex coacervate material, especially poly- Ester, natural and synthesizing polyamides, polyurethanes or polyureas.
Gelatin be it is preferable to use natural polyamide.Gelatin uses especially in the form of coacervate and complex coacervate.Out In the purpose of the present invention, the combination of the complex coacervate containing gelatin specifically gelatin and the polyeletrolyte of synthesis.Suitably The polyeletrolyte of synthesis is combined with, such as maleic acid, acrylic acid, methacrylic acid, acrylamide and Methacrylamide Unit copolymer.Particularly preferably use acrylic acid and acrylamide.Conventional hardeners can be used in capsule containing gelatin (such as formaldehyde or glutaraldehyde) hardens.It is described in detail in EP-A 0 046 535 with gelatin, the coacervate containing gelatin and is contained The complex coacervate of gelatin is encapsulated by monomer droplet.It is known for carrying out encapsulated method with synthetic polymer.Preferably Be phase interface condensation, wherein the reactive component (especially isocyanates or acid chloride) being dissolved in monomer droplet be dissolved in The second reactive component (especially amine) in water phase is reacted.
The monodisperse monomer droplet of optionally microencapsulation contains at least one initiator or the mixture of initiator (causes Agent combination) it polymerize to trigger.The initiator being preferred for according to the method for the present invention is per-compound, particularly preferred peroxidating Dibenzoyl, dilauroyl peroxide, peroxidating bis- (to chlorobenzoyls), di-cyclohexylperoxy di-carbonate, the tertiary fourth of Peroxycaprylic acid Bis- (the 2- ethylhexanoylperoxies) -2 of ester (tert-butyl peroctoate), peroxide -2-ethyl hexanoic acid tert-butyl, 2,5-, 5- dimethylhexane or t-amyl peroxy -2- ethyl hexane；And there are also azo-compound, such as 2, the bis- (isobutyls of 2 '-azos Nitrile) or 2,2 '-azos it is bis- (2- methyliso-butyronitrile).
Based on monomer mixture, initiator is preferably with by weight 0.05% to 2.5%, more preferably by weight 0.1% Amount to 1.5% uses.
Optionally the monomer droplet of monodisperse microencapsulation can also optionally contain and up to 30% (be based on by weight Monomer) crosslinking or noncrosslinking polymer.Preferred polymer is derived from above-mentioned monomer, is more preferably derived from styrene.
In the preparation of monodisperse bead polymers, in method and step a), the water phase, in another preferred embodiment In, the polymerization inhibitor of dissolution can be contained.In this case, useful inhibitor is inorganic matter or organic matter.Preferably Inorganic inhibitor is nitrogen compound, particularly preferred azanol, hydrazine, sodium nitrite and potassium nitrite, phosphite such as hydrogen phosphite Sodium and sulphur compound such as sodium dithionite, sodium thiosulfate, sodium sulfite, sodium hydrogensulfite, sodium sulfocyanate and sulphur cyanogen Sour ammonium.The example of organic inhibitor is phenolic compound, such as：Hydroquinone, hydroquinone monomethyl ether, resorcinol, adjacent benzene two The condensation product of phenol, tert-butyl catechol, pyrogallol and phenol and aldehyde.Further preferred organic inhibitor is nitrification Object.Especially preferably hydroxylamine derivative, such as N, N- diethyl hydroxylamine, N- isopropylhydroxyla and sulfonation or carboxylation N- Alkyl hydroxylamine or N, N- dialkylhydroxyamines derivative, hydrazine derivative, such as N, N- diazanyl oxalic acid, nitroso compound, example Such as the aluminium salt of N- nitrosophenyl hydroxylamine, the ammonium salt of N- nitrosophenyl hydroxylamine or N- nitrosophenyl hydroxylamine.The concentration of the inhibitor is 5- 1000ppm (being based on water phase), preferably 10-500ppm, more preferable 10-250ppm.
As already mentioned above, optionally or preferably in the presence of one or more protective colloids are in water phase, Realize the polymerization for providing the monodisperse monomer droplet of optionally microencapsulation of monodisperse bead polymers.Suitable protectiveness Colloid is natural or synthetic water-soluble polymer, preferably gelatin, starch, polyvinyl alcohol, polyvinylpyrrolidone, polypropylene The copolymer of acid, polymethylacrylic acid or (methyl) acrylic acid and (methyl) acrylate.Further preferably cellulose spreads out Biology, especially cellulose esters and cellulose ether, such as carboxymethyl cellulose, methyl hydroxyethylcellulose, methylhydroxypropyl Element and hydroxyethyl cellulose.Particularly preferred gelatin.The amount of used protective colloid is based on the water phase generally by weight Meter 0.05% to 1%, preferably by weight 0.05% to 0.5%.
In alternative preferred embodiment, the polymerization for providing monodisperse bead polymers can depositing in buffer system In lower progress.Water phase pH is the buffering of the value between 14 and 6, preferably between 12 and 8 when preferably setting polymerization beginning System.Under these conditions, the protective colloid with carboxylic acid group is completely or partially used as salt to exist.This is to these protections The effect of property colloid produces Beneficial Effect.The especially suitable buffer system of height contains phosphate or borate.In the present invention In context, term " phosphate " and " borate " further include the condensation product of the ortho position form of respective acids and salt.In water phase The concentration of phosphate or borate is 0.5-500mmol/l, preferably 2.5-100mmol/l.
Providing the agitator speed in the polymerization of monodisperse bead polymers is less key, and the pearl with routine Polymerization is compared, and is not had an impact to partial size.Using low agitator speed, these low agitator speeds are enough the monomer that will be suspended Drop is maintained at suspended state and is enough to promote the removing of heat of polymerization.Task thus, it is possible to use different type of stirrer. Specially suitable blender is that have axial movable gate stirrer.
The volume ratio of encapsulated monomer droplet and water phase is from 1:0.75 to 1:20, preferably 1:1 to 1:6.
The polymerization temperature for providing monodisperse bead polymers is instructed by the decomposition temperature of used initiator.It is usually It is between 50 DEG C to 180 DEG C, preferably between 55 DEG C and 130 DEG C.Polymerization expends 0.5 to about 20 hour.It has been found that using temperature Degree program be it is useful, wherein this starts to carry out in a low temperature of being aggregated in such as 60 DEG C, and reaction temperature is with polymerization conversion The raising of rate and improve.In this way, for example, can effectively meet to reliable reaction operation and high polymerization The requirement of conversion ratio.After polymerisation, by conventional method, such as by filtering or being decanted, by the monodisperse bead polymers point From, and optionally wash.
By means of ejector principle or crystal seed feeding principle prepare monodisperse bead polymers be it is known from the prior art, And it such as is retouched in US-A 4 444 961, EP-A 0 046 535, US 4 419 245 or WO 93/12167 It states, these patents are fully tied in the application about the preparation of the monodisperse bead polymers of the application.
Preferably monodisperse bead polymers are prepared by means of ejector principle or crystal seed feeding principle.
In method and step b), initially, amide methylating reagent is prepared.For this purpose, phthalimide is dissolved in It is mixed in solvent and with formalin.Then thus mixture is formed bis- (phthalimide-based) ethers, wherein elimination of water.It should Bis- (phthalimide-based) ethers can optionally be converted into phthalimide ester.Used in method and step b) Solvent be suitable for being swollen the atent solvent of the polymer, preferably chlorinated hydrocabon, more preferable dichloroethanes or methylene chloride.
In method and step b), which is condensed with phthalimide.Catalyst as used herein It is oleum with sulfonating agent.By means of oleum, the SO of phthalimide3Adduct is prepared simultaneously in atent solvent And carry out sulfonation.
In general, adding oleum after forming bis- (phthalimide-based) ethers and introducing pearl polymerisation thereafter Object.However, the addition can also carry out in a different order.When adding smoke after forming bis- (phthalimide-based) ethers It is preferred when sulfuric acid and thereafter introducing bead polymer.
Oleum can be with very diversified free SO3Concentration is used.By weight 24% in the concentrated sulfuric acid, The free SO of 34% and 65% concentration3It is commercially available.Particularly preferably using the free SO with by weight 65%3Ratio The oleum of example.
If using the free SO with by weight 65%3Amount oleum, used in method and step b) The amount of oleum be usually the oleum of the phthalimide 0.59g to 1.5g of every 1g but it is also possible to be smaller or It is bigger.If using the free SO with by weight 65%3Amount oleum, which is preferably every gram of phthalyl The oleum of imines 0.59g to 1.25g.
The amount of the phthalimide used in method and step b) be usually every mole of phthalimide 0.3 to 1.6mol, but can also be smaller or larger.Preferably with the phthalyl of every mole of bead polymer 0.5 to 1.1mol Imines.
Catalysis be introduced into amide methyl group and sulfonation in method and step b) 40 DEG C to 80 DEG C at a temperature of, preferably exist It is carried out at a temperature of 50 DEG C to 70 DEG C.Free SO based on 1mol phthalimide3Amount be in 0.69mol to 1.5mol Between.The free SO in method and step b) based on 1mol phthalimide3Amount be preferably 0.69mol extremely 1.2mol。
Degree of substitution in this application shows the aromatic group of bead polymer and the molar ratio of aminomethyl group.
Degree of substitution is usually 0.3 to 1.5.However, degree of substitution be also possible to it is smaller or larger.Degree of substitution be preferably 0.6 to 1.1。
Sulfonation degree in this application shows the aromatic group of bead polymer and the molar ratio of sulfonic acid group.
Sulfonation degree and the ratio of degree of substitution be usually between 0.1 to 1.0, but can also be greater or lesser.Sulfonation degree with The ratio of degree of substitution is preferably between 0.3 and 0.5.
The release of the elimination of O-phthalic acid groups and therefore aminomethyl group is in method and step c) by from 100 DEG C to 250 DEG C, preferably from 120 DEG C to 190 DEG C at a temperature of with alkali metal hydroxide (such as sodium hydroxide or potassium hydroxide) The bead polymer of the sulfonation of aqueous solution or alcoholic solution processing phthalimide methyl carries out.Sodium hydroxide solution it is dense Degree be by weight from 10% to 50%, preferably by weight from 20% to 40% in the range of.
The bead polymer of the sulfonation of obtained aminomethylation is finally with softening water washing until not alkali metal containing.
The bead polymer of the sulfonation containing aminomethyl obtained in method and step c) is converted to comprising structural element (I) The chelating resin of functional group carried out by commonly used approach well known by persons skilled in the art.
As functional group (the wherein R comprising structural element (I)1And R2It is-CH independently of one another2COOX or H, but R1And R2No Can indicate hydrogen simultaneously, and X indicates hydrogen, sodium or potassium) chelating resin of the invention preparation by from method and step c) The bead polymer of sulfonation containing aminomethyl in aqueous suspension with monoxone or derivatives thereof react progress when be preferred 's.Especially preferred chloroethene acid derivative is chloroacetic sodium salt.
The chloroacetic sodium salt preferably is used as aqueous solution.
At the reaction temperatures in 0.5 to 15 hour by the aqueous solution of chloroacetic sodium salt it is metered be initially packed into contain In the aqueous suspension of the bead polymer of the sulfonation of aminomethyl.This is metered preferably to realize in 5 to 11 hours.
The hydrochloric acid discharged in the bead polymer of these sulfonation containing aminomethyl and chloroacetic react passes through addition hydrogen Aqueous solution of sodium oxide is partially or completely neutralized, so that the pH of the aqueous suspension in this reaction is adjusted in pH Between 5 to 10.5.The reaction carries out preferably at pH 9.5.
The bead polymer of sulfonation containing aminomethyl is between 50 DEG C with 100 DEG C with chloroacetic react At a temperature of carry out.The bead polymer of sulfonation containing aminomethyl and the chloroacetic model reacted preferably between 80 DEG C and 95 DEG C It is carried out at a temperature of in enclosing.
Used suspension medium is water or aqueous saline solution.The salt considered includes alkali metal salt, especially NaCl And sodium sulphate.
As functional group (the wherein R comprising structural element (I)1And R2It is-CH independently of one another2PO(OX1)2、-CH2PO(OH) OX2Or hydrogen, but hydrogen cannot be all indicated simultaneously, and X1And X2Indicate hydrogen, sodium or potassium independently of one another) chelating tree of the invention The preparation of rouge by the bead polymer containing aminomethyl from method and step c) in the suspension of sulfur acid with and P-H- it is sour Property (according to the Mannich reaction of modification) compound, preferably with phosphorous acid, monoalkyl phosphite ester or dialkyl phosphites group The reaction of the formalin of conjunction is preferred when carrying out.
Particularly preferred use and P-H- acid compound, such as phosphorous acid or the formalin of dimethylphosphite combination.
R wherein1And R2It is independently of one another-CH2PO(OX1)2、-CH2PO(OH)OX2Or hydrogen, but cannot all indicate simultaneously Hydrogen, and X1And X2In the case where indicating hydrogen, sodium or potassium independently of one another, the bead polymer containing aminomethyl is converted to includes The chelating resin of the functional group of structural element (I) preferably in the range of from 70 DEG C to 120 DEG C at a temperature of, particularly preferably 90 DEG C with 110 DEG C between at a temperature of carry out.
As functional group (the wherein R comprising structural element (I)1And R2It is-CH independently of one another2Pyridyl group or hydrogen, but cannot All indicate hydrogen simultaneously) chelating resin of the invention preparation it is poly- by the pearl from method and step c) in method and step d) Close object in aqueous suspension with chloromethylpyridine/its hydrochloride or with 2- chloromethyl quinoline or 2- chloromethyl piperidine react into It is preferred when row.
Chloromethylpyridine/its hydrochloride can be with the shape of 2- chloromethylpyridine, 3- chloromethylpyridine or 4- chloromethylpyridine Formula uses.
As structural element (I) expression-CH2When Pyridyl residues, the reaction in method and step d) is preferably maintained by pH It is carried out while in the range of from 4 to 9, and potassium hydroxide aqueous solution or hydrogen is particularly preferably preferably added by the way that alkali is added Sodium hydrate aqueous solution progress is particularly preferably added in aqueous solution of sodium oxide.By from method and step c) containing aminomethyl Alkali is added with chloromethylpyridine or the reaction process of its hydrochloride in aqueous suspension in the bead polymer of sulfonation, will be at this PH in reaction process is preferably remained within the scope of 4-9.PH is particularly preferably maintained within the scope of 6-8.
When structural element (I) indicates aminomethyl-pyridine group, according to the reaction of method and step d) preferably at 40 DEG C to 100 It is carried out within the temperature range of DEG C, particularly preferably within the temperature range of 50 DEG C to 80 DEG C.
As functional group (the wherein R comprising structural element (I)1And R2It is-(CS) NH independently of one another2Or hydrogen, but cannot be same When all indicate hydrogen) chelating resin of the invention preparation it is poly- by the pearl of the sulfonation containing aminomethyl from method and step c) It when reacting progress is preferred with thiocarbamide or substituted thiocarbamide or rhodanate that object, which is closed, in hydrochloric suspension.It is used Suspension media be inorganic acid, preferably aqueous HCl, concentration is between by weight 10% and 40%, preferably by weight 20%- 35%.
When the element includes at least one thiocarbamide acidic-group, it is used to prepare the functional group comprising structural element (I) The reaction temperature of chelating resin of the invention be between 110 DEG C and 170 DEG C, preferably between 135 DEG C and 155 DEG C.Reaction Duration is 4 to 20 hours, preferably 8 to 15 hours.
Unexpectedly, it makes it possible to produce the packet for showing the improved absorption to metal according to the method for the present invention The chelating resin of functional group containing structural element (I).The chelating resin of these functional groups comprising structural element (I) is preferably especially It is suitable for the absorption of heavy metal, noble metal and rare earth element and their two, three or quadrivalent ion.For the purpose of the present invention Heavy metal and noble metal be preferably mercury, gallium, iron, cobalt, nickel, copper, zinc, lead, indium, cadmium, manganese, uranium, vanadium, platinum family element and gold or Silver.
Rare earth element for the purpose of the present invention be preferably scandium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, yttrium, gadolinium, terbium, dysprosium, holmium, Erbium, thulium, ytterbium, lutetium, scandium, yttrium and lanthanum and their two-, three-and/or quadrivalent ion.Functional group comprising structural element (I) Chelating resin of the invention is the absorption for being particularly preferably suitable for rare earth element.This hair of the functional group comprising structural element (I) Bright chelating resin is very particularly preferably suitable for the absorption of indium, scandium, neodymium, lanthanum and praseodymium.
Therefore the chelating resin of the invention of the functional group comprising structural element (I) is particularly well suited for use in from aqueous solution and organic Recycling and purified metal, preferably heavy metal, noble metal and rare earth element in liquid, and particularly preferred for absorption rare earth member Element and its compound.Therefore, present invention is equally related to the chelating resins of the invention of the functional group containing structural element (I) to be used for The purposes of the adsorbing metal from aqueous solution and organic liquid, preferably heavy metal, noble metal and rare earth element and its compound.
In addition, the prior art, which is proposed, prepares solar power silicon by the carbon thermal reduction of silica.In this regard, WO 2007/106860 A1 for example proposes to be reacted by the carbon source with high-purity that high-purity silica gel is converted into solar power silicon.With The high-purity silicon dioxide needed for carrying out such method is preferably prepared and reacting silicate solutions with acidulant, at it Also chelating resin is used in context, preferably comprises chelating resin of the phosphonic acids/phosphonate groups as functional group.Therefore the present invention It equally include that the chelating resin of the invention of the functional group comprising structural element (I) is being used to prepare and is purifying silicon, preferably having Purposes in the method for the silicon of purity greater than 99.99%.Being used to prepare and purify the method for silicon, it is preferable to use want comprising structure The chelating resin of the functional group of plain (I), wherein at least one group R1Or R2It is=- CH independently of one another2PO(O X1)2Or- CH2PO(OH)OX2, and X1And X2Hydrogen, sodium or potassium are indicated independently of one another.
Make it possible to prepare economy with specific characterization of adsorption, novelty, stable according to the method for the present invention for the first time The chelating resin of sulfonation.
The analysis of chelation group and highly acid sulfonic acid group measures
The measurement of amount-total capacity (TC) of the chelation group of resin
100ml exchanger is filled into Filter column and is eluted with by weight 3% hydrochloric acid in 1.5 hours.So Afterwards with softening water washing column until effluent is neutral.
The 50ml regenerating ion exchanger in column is set to be subjected to 0.1N sodium hydroxide solution.In each case by effluent It collects in 250ml graduated cylinder, and whole amount is titrated with 1N hydrochloric acid for methyl orange.
Continue to feed until 250ml effluent is consumed with the 1N hydrochloric acid of 24.5-25ml.Once the test has terminated, Measurement is in the volume of the exchanger of Na form.
Total capacity (TC)=(X25- Σ V) -3 exchanger in terms of mol/l
The number of X=effluent part
The wastage in bulk or weight in terms of ml of 1N hydrochloric acid of the Σ V=during the titration of effluent.
The measurement of the amount of strong acid group
TC-Na+ form
100ml exchanger is measured on making stereometer firm by ramming and is flushed in chimney filter under water in DM.Then,
By 1000ml sodium chloride solution, w (NaCl)=10% is filtered through.
Then the exchanger is rinsed out with DM water with identical flow velocity, until having been carried out neutral reaction.It is mixed with methyl orange The 100ml washing water effluent of conjunction should have sodium hydroxide c (NaOH)=0.1mol/L consumption no more than 0.1ml.
Then,
50ml exchanger is measured on making stereometer firm by ramming and is flushed in chimney filter under water in DM.Then,
By 300ml hydrochloric acid, w (HCl)=15% is filtered through.
Then the exchanger is rinsed out with DM water, until having been carried out neutral reaction.The 100ml mixed with methyl orange is washed Sodium hydroxide c (NaOH)=0.1mol/L consumption no more than 0.1ml should be had by washing water effluent.
Then,
By 950ml sodium chloride solution, w (NaCl)=2.5% is filtered through.Effluent is collected in 1000ml measuring bottle And it is mended with DM water to scale.
Solution that 10ml is thoroughly mixed is diluted in 300ml conical flask with the DM water of about 90ml and with sodium hydroxide water Solution c (NaOH)=0.1mol/l is titrated to yellow from red/orange for methyl orange.One liter of DM of the exchanger is washed It washs and then measures volume.
TC-H form
For the exchanger of H-shaped formula, TC is measured in and without regenerated situation.
Form placement that 50ml is supplied and
With 100ml mixed bed water washing.
Then, make the sodium chloride solution of 950ml, w (NaCl)=2.5% is passed through.
Then by one liter of DM water washing of the exchanger and the exchanger is used
300ml hydrochloric acid, w (HCl)=15%, the H-shaped formula being converted into as described at the beginning of the program.The acid is rinsed Fall and make the sodium chloride solution of other 950ml, w (NaCl)=2.5% is passed through.
It calculates
Example 1
The preparation of the monodisperse macroporous bead polymer of styrene-based, divinylbenzene and ethyl styrene
10 liters of glass reactor is initially packed into 3000g softened water, and 10g gelatin, 12 hypophosphite monohydrate of 16g is added Solution in 320g deionized water of disodium hydrogen and 0.73g resorcinol is simultaneously mixed.Balance the mixture to 25 DEG C.With Afterwards, under stiring, the mixture of the monomer droplet of the microencapsulation of 3200g is added, these drops have narrow particle diameter distribution, by By weight 5% divinylbenzene and by weight 1% ethyl styrene (with 80% divinylbenzene can quotient The form use of the isomer mixture of the divinylbenzene and ethyl styrene of purchase), by weight 0.4% diphenyl peroxide Acyl, by weight 56.3% styrene and by weight 37.5% Permethyl 99A (have high proportion five methylheptane Industrial isomer mixtures) composition, which is made of the complex coacervate that formaldehyde hardens, the complex coacervate by gelatin with And the copolymer composition of acrylamide and acrylic acid；And 3200g, which is added, has 12 water phase of pH.
The mixture is stirred and by according in 25 DEG C of beginnings and in the 95 DEG C of temperature program(me) terminated raising temperature Polymerize the mixture to completion.The mixture is cooling, it carries out washing and then subtracting at 80 DEG C on 32 μm of sieve It press dry dry.
This provides the 1893g monodisperse bead polymers with smooth surface.
The monodisperse bead polymers have the appearance of chalk color and the heap density of about 390g/l.
It also include SO3The preparation-of the resin of the phthalimide methyl of H group is in phthalimide methyl Dissociate SO during change3Molar ratio with phthalimide is 0.7 to 1
By 419.3g phthalimide, 1410g 1,2- dichloroethanes (DCE) and 242.5g by weight 30% Formalin is initially fitted into four-neck flask at room temperature and is heated to boiling point.
When starting to flow back (about 70 DEG C), with sodium hydrate aqueous solution, pH is adjusted to pH 5.5- by ω (NaOH)=50% 6.0.The mixture is boiled 30 minutes at the boiling point.Then it goes to remove water.Then 30.7g monohydrate is added at about 70 DEG C.
Then it goes to remove water again, until obtaining ether.Then the mixture is stirred at room temperature up to 12 hours, and Then the metered 245.7g oleum at 25 DEG C -30 DEG C, ω (free SO3)=65%.
Then monodisperse pearl polymerisation of the 317.1g from example 1 in the DCE of 1000ml is added at 30 DEG C -40 DEG C Object.The mixture is stirred into 6.5h at 65 DEG C.
The DCE liquid is siphoned away via filter suction pipe, the DM water (70 DEG C of highest) that filtrate is preheated is repulped, and Remaining DCE is distilled.
Then the resin is rinsed out with DM water.
Volumetric production=1900ml resin
Dry weight=0.3932g/ml
Elemental analysis：
Nitrogen content：By weight 5.0%
Sulfur content：By weight 3.1%
Further include SO3The preparation of the resin containing aminomethyl of H group
By 2100ml come from example 2a) resin, by the sodium hydrate aqueous solution and 2140ml of 767g by weight 50% Water preparation 2520ml sodium hydrate aqueous solution be fitted into 6l-VA- autoclave at room temperature.
Then the autoclave is heated in 2 hours until 180 DEG C with 200rpm.
The autoclave is kept 8 hours at this temperature.
After cooling, by test product DM water washing until neutral.
Volumetric production=1571ml
The form A l form OH form that HCl number is supplied
1.29mol/l 30ml 38ml 31ml
Washing water=>0.5l/30ml
Replace=0.63
Dry weight=0.2696g/ml
It comprising AminomethylphosphoniAcid Acid group and also include SO3The preparation of the resin of H group
Resin of the 1520ml from example 2b) is initially packed into round-bottomed flask at room temperature together with the DM water of 759ml. Then 701.6g dimethylphosphite is added dropwise in 15min, and the mixture is stirred for 15min.Then it is counted in 2 hours The sulfuric acid of 1962g by weight 98% is added in amount.Then the mixture is heated to 95 DEG C.Then 716g is added dropwise at 95 DEG C to press The formalin of poidometer 30%.At 95 DEG C, which is stirred for 4 hours.After cooling, by resin DM water Washing is until neutral.
Volumetric production=1870ml
By the resin sodium hydrate aqueous solution, ω (NaOH)=4% is converted into free alkali form.
Volumetric production=2680ml
NaOH number：2.78mol/l
The presence for chelating AminomethylphosphoniAcid Acid group is reflected by NaOH number.There are 2.78mol ammonia first for every liter of final product Base phosphonyl group.
NaCl number：0.79
The presence of highly acid sulfonic acid group is reflected by the sulfur content of NaCl number and by weight 5.0%.
There are 0.79mol sulfonic acid groups for every liter of final product.
It is made up of the final product of elemental analysis
ω (N)=by weight 4.6% ω (P)=by weight 8.3% ω (O)=by weight 27.0% ω (S)= By weight 5.0%
Table 1
The summary of result from example 1

Claims (15)

1. the chelating resin of functional group of the one kind comprising structural element (I)
WhereinIndicate polymer backbone and R1And R2Expression-CH independently of one another2COOX、-CH2PO(OX1)2、-CH2PO (OH)OX2、-(CS)NH2、–CH2Pyridyl group or hydrogen, wherein R1And R2It cannot all be simultaneously hydrogen and X, X1、X2It is independent of one another with Y Ground indicates hydrogen, sodium or potassium.
2. as described in claim 1 includes the chelating resin of the functional group of structural element (I), wherein R1And R2Independently of one another It is-CH2PO(OX1)2、-CH2PO(OH)OX2Or hydrogen, and X1And X2Hydrogen, sodium or potassium are indicated independently of one another.
3. a kind of preparation method of the chelating resin of the functional group comprising structural element (I) as described in claim 1, feature It is, this method includes
It a) will by least one single-ethenyl aromatic compound and at least one polyvinyl aromatics and at least The monomer droplet that a kind of initiator or initiator combination are constituted is converted into bead polymer,
B) make the bead polymer phthalimide methylization simultaneously with phthalimide in the presence of oleum And sulfonation, wherein free SO3Phthalimide of the amount based on 1mol be at least 0.69mol,
C) bead polymer of the sulfonation of phthalimide methyl is converted to the pearl polymerisation of the sulfonation of aminomethylation Object, and
D) bead polymer of the sulfonation of the aminomethylation is made to react to provide the chela of the functional group comprising structural element (I) Resin.
4. the preparation method of the chelating resin of the functional group comprising structural element (I), feature exist as claimed in claim 3 In the bead polymer in step a) is prepared in the form of monodisperse and therefore prepares monodispersed chelating resin.
5. the preparation method of the chelating resin of the functional group comprising structural element (I) as described in claim 3 or 4, feature It is, the free SO in step b)3Phthalimide of the amount based on 1mol be between 0.69mol and 1.5mol.
6. the preparation method of the chelating resin of the functional group comprising structural element (I), feature exist as claimed in claim 3 In free SO in step b)3Phthalimide of the amount based on 1mol be between 0.69mol and 1.2mol.
7. the chelating resin of functional group of the one kind comprising structural element (I), the chelating resin are prepared as claimed in claim 3.
8. the purposes that chelating resin as claimed in claim 1 or 7 is used for adsorbing metal.
9. purposes as claimed in claim 8, which is characterized in that the absorption of the metal is carried out from aqueous solution or organic liquid 's.
10. the purposes as described in any one of claim 8 and 9, which is characterized in that the metal is selected from the group of the following terms：Mercury, Gallium, iron, cobalt, nickel, copper, zinc, lead, indium, cadmium, manganese, uranium, vanadium, platinum family element and gold or silver, or it is selected from rare earth element.
11. purposes as claimed in claim 8, which is characterized in that the metal is rare earth element.
12. purposes as claimed in claim 11, which is characterized in that the rare earth element be cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, Dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium and lanthanum.
13. purposes as claimed in claim 8, which is characterized in that the metal is selected from the group of the following terms：Indium, scandium, neodymium, lanthanum and Praseodymium.
14. the chelating resin of the functional group as claimed in claim 1 or 7 comprising structural element (I) is used to prepare and purifies silicon Purposes.
15. the purposes of chelating resin as claimed in claim 14, which is characterized in that chelating resin includes structural element (I) Functional group, wherein R1And R2It is-CH independently of one another2PO(OX1)2Or-CH2PO(OH)OX2, and X1And X2Earth's surface independent of one another Show hydrogen, sodium or potassium.
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